Tungsten pentachloride conditioning and crystalline phase manipulation

ABSTRACT

Conditioning of tungsten pentachloride to form specific crystalline phases is disclosed. The specific crystalline phases permit stable vapor pressures over extended periods of time during vapor deposition and etching processes.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.15/966,924, filed Apr. 30, 2018, the entire contents of which areincorporated herein by reference.

TECHNICAL FIELD

Conditioning of tungsten pentachloride to form specific crystallinephases is disclosed. The specific crystalline phases permit stable vaporpressures over extended periods of time during vapor deposition andetching processes.

BACKGROUND

WCI₅ has attracted interest as CVD or ALD materials used to depositW-containing films, such as W metal; WSi₂; WX₂, in which X is S, Se, orTe; W-doped amorphous Carbon, WO₃, etc. (see, e.g., U.S. Pat. Nos.9,595,470; 9,230,815, and 7,641,886 and US Pat App Pub Nos 2003/190424and 2017/350013).

The crystal structure of WCI₅ has been reported in Acta Crystallogr.(1978) B34, pp.2833-2834. Its powder X-ray diffraction pattern wascollected as International Centre for Diffraction Data PowderDiffraction File (PDF) card # 04-005-4302. Okamoto reported the W-CIphase diagram. Journal of Phase Equilibria and Diffusion, Vol. 31, No. 4(2010).

WO2017/130745 to JX Nippon Mining & Metals Corp discloses a high puritytungsten pentachloride synthesis method.

WO2017/075172 to L'Air Liquide, Societe Anyonyme pour l'Etude etl'Exploitation des Procedes Georges Claude discloses a vessel havinginternally wettable surface therein coated with one or more barrierlayers to, for example, inhibit contamination of a material, such as ametal halide, contained in the vessel.

WCI₅ suffers from being a solid, low vapor pressure precursor. Providinga sufficient flux to the processing chamber from a solid, low pressureprecursor like WCI₅ is difficult. Another challenge is to maintain astable flux of precursor as the WCI₅ containing package is beingdepleted. Both aspects are common to all solids, and may be addressed byusing solid-specific packaging (see, e.g., US Pat App Pub Nos2009/0181168 and 2017/0335450).

A need remains to supply a stable and reproducible flux of WCI₅ vaporsto a vapor deposition or etching process chamber over extended periodsof time.

SUMMARY

Disclosed are methods of conditioning WCI₅ to produce a WCI₅-containingcompositions comprising approximately 10% weight to approximately 40%weight of phase 1 WCI₅ as determined by X-ray diffraction. A containerof WCI₅ is heated to a temperature ranging from approximately 190° C. to245° C. for a time period ranging from approximately 2 hours toapproximately 48 hours. The disclosed methods may include one or more ofthe following aspects:

-   -   the container being selected to be non-reactive to WCI₅;    -   the container being glass;    -   the container being a glass-coated container;    -   the container designed to prevent direct contact between WCI₅        and stainless steel;    -   the time period ranging from approximately 24 hours to        approximately 48 hours;    -   the time period ranging from approximately 40 hours to        approximately 48 hours;    -   the temperature ranging from approximately 205° C. to 240° C. ;    -   the temperature ranging from approximately 215° C. to 235° C. ;    -   the WCI₅-containing composition comprising approximately 10%        weight to approximately 35% weight of Phase 1 WCI₅;    -   the WCI₅-containing composition comprising approximately 10%        weight to approximately 30% weight of Phase 1 WCI₅;    -   the WCI₅-containing composition comprising approximately 10%        weight to approximately 25% weight of Phase 1 WCI₅;

Also disclosed are the WCI₅-containing compositions conditioned by themethods disclosed above. The WCI₅-containing compositions haveapproximately 10% weight to approximately 40% weight of Phase 1 WCI₅ asdetermined by X-ray diffraction. The disclosed WCI₅-containingcompositions may contain one or more of the following aspects:

-   -   the WCI₅-containing material having approximately 10% weight to        approximately 35% weight of Phase 1 WCI₅;    -   the WCI₅-containing material having approximately 10% weight to        approximately 30% weight of Phase 1 WCI₅;    -   the WCI₅-containing material having approximately 10% weight to        approximately 25% weight of Phase 1 WCI₅.

Also disclosed are methods of providing a stable vapor pressure of WCI₅over a time period by subliming a WCI₅-containing composition comprisingapproximately 10% weight to approximately 40% weight of Phase 1 WCI₅ asdetermined by X-ray diffraction. The WCI₅-containing compositionsconditioned by the methods disclosed above is introduced into a solidprecursor vaporizer. The solid precursor vaporizer is connected to thesemiconductor processing chamber and heated to a temperature for thetime period to deliver a steady supply of WCI₅ vapor. The disclosedmethods may include one or more of the following aspects:

-   -   the container being selected to be non-reactive to WCI₅;    -   the container being glass;    -   the container being a glass-coated container;    -   the container designed to prevent direct contact between WCI₅        and stainless steel;    -   the temperature ranging from approximately 100° C. to 150° C.;        the time period ranging from approximately 60 minutes to        approximately 16 hours;    -   the time period ranging from approximately 24 hours to        approximately 48 hours;    -   the time period ranging from approximately 40 hours to        approximately 48 hours;    -   the WCI₅-containing composition comprising approximately 10%        weight to approximately 35% weight of Phase 1 WCI₅;    -   the WCI₅-containing composition comprising approximately 10%        weight to approximately 30% weight of Phase 1 WCI₅;    -   the WCI₅-containing composition comprising approximately 10%        weight to approximately 25% weight of Phase 1 WCI₅.

Notation and Nomenclature

Certain abbreviations, symbols, and terms are used throughout thefollowing description and claims, and include:

As used herein, the indefinite article “a” or “an” means one or more.

As used herein, the terms “approximately” or “about” mean ±10% of thevalue stated.

As used herein, the term “comprising” is inclusive or open-ended anddoes not exclude additional, unrecited materials or method steps; theterm “consisting essentially of” limits the scope of a claim to thespecified materials or steps and additional materials or steps that donot materially affect the basic and novel characteristics of the claimedinvention; and the term “consisting of” excludes any additionalmaterials or method steps not specified in the claim.

As used herein, the abbreviation “RT” means room temperature or atemperature ranging from approximately 18° C. to approximately 25° C.

As used herein, the abbreviation “XRD” means X-Ray Diffraction and“PXRD” means Powder X-Ray Diffraction,

As used herein, the abbreviation “ALD” means Atomic Layer Deposition andthe abbreviation “CVD” means Chemical Vapor Deposition.

As used herein, any reference to WX₅ includes the monomeric WX₅, thedimeric W₂X₁₀, and combinations thereof.

The standard abbreviations of the elements from the periodic table ofelements are used herein. It should be understood that elements may bereferred to by these abbreviations (e.g., W refers to tungsten, Sirefers to silicon, C refers to carbon, etc.).

Any and all ranges recited herein are inclusive of their endpoints(i.e., x=1 to 4 or x ranges from 1 to 4 includes x=1, x=4, and x=anynumber in between), irrespective of whether the term “inclusively” isused.

BRIEF DESCRIPTION OF THE FIGURES

For a further understanding of the nature and objects of the presentinvention, reference should be made to the following detaileddescription, taken in conjunction with the accompanying FIGS.

FIG. 1 is an X-Ray Diffraction (XRD) graph of % relative intensityversus the °2θ position of Phase 1 WCI₅ (copper radiation);

FIG. 2 is an XRD graph of % relative intensity versus the °2θ positionof Phase 2 WCI₅ (copper radiation);

FIG. 3 is a graph showing the % mass loss at 120° C. versus time fordifferent crystalline phase WCI₅ samples;

FIG. 4 is a graph of the sublimation rate in mass loss%/minute versusthe percentage of Phase 1 WCI₅;

FIG. 5 is a graph showing the sublimation rate (Δ mass/Δ time) versustime for two different crystalline phase WCI₅ samples; and

FIG. 6 is a schematic diagram of exemplary equipment in which Example 6was performed.

DESCRIPTION OF PREFERRED EMBODIMENTS

Applicants have discovered that the sublimation rate from WCI₅ subjectto normal industrial sublimation conditions gradually decreases, leadingto performance drift in processes that utilize WCI₅ vapors, In otherwords, the process rate (i.e., deposition or etching rate) using a newcanister is faster than the process rate after a portion of the samecanister has been used.

Further analysis demonstrates that the change in performance is due tothe change in the relative fraction of the crystalline phases of WCI₅.More particularly, as shown in Example 1, the crystalline phase offreshly sublimed WCI₅ tends to comprise greater than 95% of one WCI₅crystalline phase (“Phase 1”). However, during the vapor depositionand/or etching process, the canister of WCI₅ is heated to a temperatureof approximately 150° C. (see, e.g., Example 3 of PCT Pat App PubWO2017/075172). As shown in Example 3 of the present application, thepercentage of Phase 1 WCI₅ drops to approximately 35% after 120 days at120° C.

To Applicant's knowledge, the crystal structure of Phase 1 has not beenreported. Phase 1 of WCI₅ is monoclinic with space group 12 as C2/m. Theunit cell parameters are a=18.11 Å, b=17.72 Å, c=5.809 Å, and β=90.35°.Phase 1 of WCI₅ is isostructural to reported compounds NbCl₅ (PXRDpattern: ICDD PDF Card #04-0005-4229, for structure see Ref ActaCrystallogr. 1958, 11, pp. 615-619) and TaCl₅ (PXRD pattern: ICDD PDFCard #04-109-4194, for structure see Ref Anorg Allg Chem., 2001, 627,pp. 180-185). The crystal structure for Phase 1 may be generated bymodifying the unit cell parameters of NbCl₅ or TaCl₅ with the above unitcell parameters obtained from PXRD data. The corresponding Nb or Taatoms are then replaced with W atoms. The simulated PXRD data may begenerated using software such as Mercury or CrystDiffract software. FIG.1 is the simulated PXRD spectrum of Phase 1 generated using the Mercurysoftware.

The PXRD pattern and crystal structure of Phase 2 of WCI₅ have beenpreviously reported at ICDD PDF Card #04-005-4302 and Acta Crystallogr.1978, B34, pp. 2833-2834. Similar to Phase 1, Phase 2 is monoclinic withspace group 12 as C2/m. The unit cell parameters are a=17.438(4) Å,b=17.706 Å, c=6.063(1) Å, β=95.51(2)°. FIG. 2 is the simulated PXRDspectrum of Phase 2 from its crystal structure. The simulated PXRDpattern of FIG. 2 is identical to the one deposited in the ICDDdatabase.

TABLE 1 X Ray Diffraction Simulation Data for Phase 1 and Phase 2 WCI₅Phase 1 Phase 2 2 Theta (°) Relative Intensity % 2 Theta (°) RelativeIntensity % 9.956 10.61 9.983 14.41 14.666 8.11 15.486 100.00 15.87378.98 16.103 100.00 16.76 28.44 16.76 14.51 17.059 11.31 18.062 15.3618.862 41.84 20.013 31.43 20.043 35.64 21.002 15.27 21.316 13.71 21.4915.12 24.063 19.92 24.952 6.82 27.119 13.19 27.532 23.52 29.55 23.6230.21 4.67 33.039 20.68 33.459 8.25 33.82 27.15 40.24 20.65 42.971 9.1045.98 13.58

In solid state, both crystalline phases contain the dimer of WCI₅ (i.e.,W₂Cl₁₀). Each tungsten atom is in a pseudo-octahedral geometry connectedto four non-shared Cl atoms and two shared Cl atoms. As a result, thephase conversion from Phase 1 to Phase 2 is a diffusionlesstransformation. In other words, no major reorganization of the crystalstructure is observed. In diffusionless transformations, the atomschange their positions slightly in a relatively coordinated mannerwithout interruption of the original bonding (see, e.g., D. A. Porter etal., Phase transformations in metals and alloys, Chapman & Hall, 1992,p. 172). More particularly, phase conversion between Phase 1 and Phase 2WCI₅ mainly involves a change of the β angle of the unit cells, withslight distortions on other unit cell parameters.

As shown in the examples that follow, different methods were used toprepare WCI₅ containing different percentages of Phase 1 and Phase 2.Powder X-Ray Diffraction (PXRD) measurements were performed on a RigakuMiniflex diffractometer (Cu Kα radiation, λ=1.5406 Å). One of ordinaryskill in the art will recognize that the PXRD measurements may also bedetermined using other anodes, including but not limited to Co, Mo, Cr,Ni, etc. The diffractometer was housed in a nitrogen filled glovebox sothat the air-sensitive materials were handled without air/moistureexposure. Samples were received and transferred into the glovebox. Vialscontaining WCI₅ were then opened, and the materials ground into finepowders with an agate mortar and pestle. Standard sample holders wereused. X-ray output was 450 W, and the detector was a scintillationcounter. The powder patterns were collected using a θ-θ scan mode (range2 θ=8°-50°, step size of 0.02°).

The Rietveld method and reference crystal structures of FIGS. 1 and 2were used to determine the percentage of each crystalline phase in avariety of WCI₅ samples. More particularly, the background wasdetermined and removed from each data set. The remaining diffractionpeaks were matched to the reference patterns of FIGS. 1 and 2 todetermine the phase composition percentage. To be specific, for thePhase 1/Phase 2 WCI₅ mixtures, diffraction peaks from the XRD data werematched to reference patterns for Phase 2 WCI₅ (PDF #04-005-4302) andTaCl₅ (PDF #04-019-4194, isostructural to the unreported Phase 1 WCI₅,substitute Ta with W atoms and adjust unit cell parameters to yield thecrystal structure of Phase 1 WCI₅). The XRD data were then used todetermine the relative phase fractions of the two crystalline phases ineach sample. The final fits of the calculated diffraction intensitiesfrom the refined sample model to the raw XRD data was performed. Thecomputer generated data closely matches the experimental data. Refinedphase fractions may be obtained using software, such as MDl-Jade 2010.

Applicants have discovered that the Phase 1 and Phase 2 crystallinephases of WCI₅ have different vapor pressures. FIG. 3 is a graph showingthe showing the % mass loss over 60 minutes at 120° C. for differentcrystalline phase WCI₅ samples. In FIG. 3, the solid line (

) shows the 0.0311% mass loss/minute for 96% Phase 1 WCI₅; the longdash-dot line (

) shows the 0.029% mass loss/minute for 83% Phase 1 WCI₅; the shortdash-dot line (

) shows the 0.0261% mass loss/minute for 67% Phase 1 WCI₅; the longdash-long dash line (

) shows the 0.0248% mass loss/minute for 40% Phase 1 WCI₅; the shortdash-short dash line (

) shows the 0.0239% mass loss/minute for 39% Phase 1 WCI₅; and thedotted line H shows the 0.0223% mass loss/minute for 22% Phase 1 WCI₅.The difference between the 0.0311% mass loss/minute for 96% Phase 1 WCI₅versus the 0.0223% mass loss/minute for 22% Phase 1 WCI₅ demonstratesthe impact that the phase change may have on the vapor supply andaccompanying process rate.

FIG. 4 is a graph of the sublimation rate in mass loss %/minute versusthe percentage of Phase 1 WCI₅. As can be seen, the sublimation rate islinearly proportional to the percentage of crystalline phase material.

FIG. 5 is a graph showing the sublimation rate (Δ mass/Δ time) versustime for two different crystalline phase WCI₅ samples. The blacktriangles show that the sublimation rate for 22% Phase 1/78% Phase 2WCI₅ is linear. This graph shows that the sublimation rate decreasesonly slightly during 16 hours of sublimation. In contract, the cleardiamonds show that the sublimation rate for 96% Phase 1/4% Phase 2 WCI₅almost immediately begins to rapidly decrease.

As can be seen from FIGS. 3-5, samples containing higher concentrationsof Phase 2 have a lower sublimation rate in comparison to samplescontaining higher concentrations of Phase 1. Therefore, Phase 1 has ahigher vapor pressure than Phase 2. Supplying WCI₅ that contains amixture of Phase 1 and Phase 2 crystalline material will cause a vaporpressure drift over time because Phase 1 depletes faster than Phase 2(i.e., Phase 1 has a higher vapor pressure), even in the absence of anyphase conversion. Additionally, as shown in Example 3, Phase 1 convertsto Phase 2 during the vapor deposition or etching processes. Thisconversion further exacerbates the vapor pressure drift.

The difference in vapor pressures and the conversion of the Phase 1 WCI₅to Phase 2 WCI₅ during semiconductor processes results in shortened useof the WCI₅ materials and the necessity to adjust equipment parametersin order to be able to maintain a stable supply of WCI₅ vapors to thevapor deposition tool. Needless to say, adjusting parameters duringsemiconductor manufacturing is not desired.

To maintain a stable vapor pressure over time, the Phase 1:Phase 2 ratioshould be maintained as close to the original phase ratio as possible.Additionally, Applicants have discovered that the Phase 2 material doesnot convert back to Phase 1 under storage at room temperature or afterbeing heated to temperatures no greater than 247° C. As a result, vaporsfrom Phase 2 WCI₅ may be supplied at a variety of temperatures withoutchanging crystallinity phase. Therefore, even though the vapor pressureof Phase 2 is lower than that of Phase 1, a stable supply of the WCI₅vapor may be supplied using higher concentrations of Phase 2 WCI₅. Thestable supply of WCI₅ vapor is beneficial for semiconductor processes,such as vapor deposition or etching. Unfortunately, Applicants have notbeen able to create 100% Phase 2 WCI₅.

WCI₅ may be heated to a temperature just below its melting point inorder to convert it from predominantly Phase 1 material to predominantlyPhase 2 material (i.e., melting point=248° C.). The phase conversionoccurs faster at the higher temperatures (i.e., faster at 240° C. thanat 210° C.). Applicants have been able to produce WCI₅ compositionscontaining approximately 10% weight to approximately 40% weight of Phase1 WCI₅ as determined by PXRD using a Cu anode, preferably containingapproximately 10% weight to approximately 35% weight of Phase 1 WCI₅,and more preferably containing approximately 10% weight to approximately25% weight of Phase 1 WCI₅.

Interestingly, WCI₅ maintains a higher percentage of Phase 1 materialwhen it is melted and cooled (i.e., greater than 30%), as shown inExample 4. Similarly, as shown in Example 3, approximately 35% of Phase1 material remains after consumption over 120 days at 120° C.

The phase conversion that typically occurs during the vapor depositionprocess (i.e., at temperatures of approximately 150° C.) occurs muchslower than the phase conversion that occurs between 190° C. and 245° C.During the vapor deposition process, the vapors of WCI₅ are typicallygenerated using a solid precursor vaporizer heated to a temperature ofapproximately 150° C. See, e.g., WO2017/075172 to L'Air Liquide, SocieteAnyonyme pour l'Etude et l'Exploitation des Procedes Georges Claude. Thesolid precursor vaporizer is typically a stainless steel vessel, with atleast an inlet and an outlet connected to isolation valves. Heating thesolid precursor vaporizer to temperatures of 150° C. for an extendedperiod of time in order to convert the material from Phase 1 to Phase 2may result in corrosion and contamination of the WCI₅ by any stainlesssteel elements, such as Cr, Fe, Ni, etc.

One of ordinary skill in the art will recognize that the any linesconnecting the solid precursor vaporizer to the deposition or etchingchamber need to be heated in order to maintain the gas phase of theprecursor. Failure to do so will result in precipitation of the solidprecursor onto the lines. For cost, safety, and maintenance reasons,semiconductor manufacturers prefer to maintain the solid precursorvaporizer and any lines connecting the vaporizer to the processingchamber at lower temperatures (and preferably at room temperature).This, of course, further exacerbates the sublimation issues discussedabove (i.e., depletion of the higher vapor pressure Phase 1 material andslow conversion of any remaining Phase 1 material to Phase 2).

Performing the phase conversion in a separate vessel at temperaturesranging from approximately 190° C. to 245° C. enables faster phaseconversion than any conversion that occurs during the vapor deliveryprocess. The vessel is chosen to withstand the both the material and itsproperties when heated. The vessel is also chosen to limit the risk ofimparting any impurities into the WCI₅. Suitable vessels include glassvessels, quartz vessels, glass coated vessels, etc. After the WCI₅ isconverted to a majority of Phase 2 material, it may be filled into asolid precursor vaporizer for use in the vapor deposition process.

EXAMPLES

The following non-limiting examples are provided to further illustrateembodiments of the invention. However, the examples are not intended tobe all inclusive and are not intended to limit the scope of theinventions described herein.

Example 1: Vacuum Sublimation

Equipment: Glass sublimator set (Bottom part, cold finger, 0-ring,clamp, chiller)

Crude WCI₅ was added to the bottom of the glass sublimator set. Thesublimator was then placed into the heating mantle and properlyassembled. The chiller was maintained at the coolant temperature atapproximately 6° C. to approximately 25° C. The heating mantle wasmaintained at approximately 200° C. to approximately 220° C. Afterheating, the heating mantle is turned off and allowed to cool. Thesublimator set was carefully disassembled and the materials condensed onthe cold finger are then collected. Samples are submitted for XRDanalysis to quantify crystalline phases.

This process is similar to that disclosed in WO2017/130745 to JX NipponMining & Metals Corp, in which the sublimate is recovered by air coolingor water cooling. Applicants believe that Phase 1 WCI₅ forms on the coolsurface of the cold finger or other chilled surface.

TABLE 2 Batch Ph1 (%) Ph2 (%) Batch 1 97 3 Batch 2 98 2 Batch 3 96 4Batch 4 97 3 Batch 5 95 5 Batch 6 92 8

Example 2: Carrier Gas Assisted Sublimation

Crude WCI₅ was loaded to the coated stainless steel bottom kettle of asublimation system. A lid was secured to the kettle with a clamp. Aheating mantle was placed on the lid. One KF 45 joint of stainless steeltubing was connected to the lid with a KF 45 Kalrez gasket and securedwith a clamp. A separate KF 45 joint of stainless steel tubing wasconnected to the inlet port of the lid. A vacuum line was connected tothe outlet port of the lid. A N₂ carrier gas line was connected to thesublimator's purging port.

After a leak test of the system, the temperature controllers were setto:

-   -   Bottom: 210+/−10° C.    -   Lid: 220+/−10° C.    -   Transfer tubing: 230+/−10° C.    -   Receiving pot lid: 240+/−10° C.    -   N₂ flow: 100+/−10° C.

The flow meter for N₂ was set to 0.200 L/min.

After heating, the heating mantles were turned off. The sublimator wascooled below 80° C. and then flow of the carrier gas N₂ was stopped. Thereceiving pot is carefully disassembled and solid materials collected.Samples are submitted for XRD analysis to quantify crystalline phases.

TABLE 3 Batch Ph1 (%) Ph2 (%) Batch 1 68 32 Batch 2 56 44 Batch 3 83 17Batch 4 57 43As can be seen, this process produces less Phase 1 WCI₅ than the processof Example 1. Applicants believe that the cooling temperatures affectthe crystallinity of the final WCI₅ product. In other words, Applicantsbelieve that cooler temperatures produce more Phase 1 WCI₅. Thecondensing temperature of Example 2 is higher than that of Example 1because no external cooling source was used. Therefore, the percentageof Phase 1 material is higher in Example 1 than Example 2.

Example 3: In Situ Phase Change

Freshly vacuum sublimed WCI₅ is added to a solid precursor deliverydevice and maintained at a temperature of approximately 120° C. As shownin Example 1, such freshly sublimed WCI₅ contains greater than 90% Phase1 WCI₅. Table 4 demonstrates that the percentage of Phase 1 materialdecreases due to the vapor deposition or etching processing conditions.More particularly, after more than 50% of the material has been consumedduring the vapor deposition or etching process, only 35-51% of Phase 1WCI₅ remains. However, WCI₅ containing less than 35% Phase 1 WCI₅ hasnot been produced during the vapor deposition process. Applicantsbelieve that standard sublimation conditions are not sufficient toproduce high quantities of Phase 2 WCI₅.

TABLE 4 Initial Final % (w/w) % Phase 1 % Phase 2 Batch Weight (g)Weight (g) Consumed Remaining Remaining 1 402 109 73 35 65 2 404 146 6440 60 3 400 168 58 49 51 4 400 171 57 51 49

Example 4: Melting

In a glovebox, 15 grams of freshly sublimed WCI₅ produced by the methodof Example 2 (with 71% P1 and 29% P2) was added to a 100 mL heavy wallglass pressure vessel. The pressure vessel was sealed and removed fromthe glovebox. The bottom of the pressure vessel was submerged in apre-heated sand bath at 260° C. in order to heat WCI₅ above its meltingpoint (i.e., 248° C.). Once the solid WCI₅ completely melted, thematerial was heated for another 5 minutes, followed by cooling underdifferent conditions. The pressure vessel was brought back into theglovebox, The WCI₅ product was collected and submitted for XRD analysisto quantify crystalline phases.

TABLE 5 Sample Condition Ph1 (%) Ph2 (%) W-FG1717 Starting Materials 7129 18-001-D Rapid cooling (remove from heat 38 62 bath to allow rapidcooling to RT) 18-003-A Slow cooling to 190 C. for 1 hr 32 68 (leave in190 C. bath for 1 hr to allow slow cooling, then remove to allow rapidcooling to RT)As can be seen, melting and cooling, whether quickly or more slowly,produces Phase 1=30-40%; Phase 2=70-60%.

Example 5: Small Scale Conditioning

In a glovebox, 15 grams of freshly sublimed WCI₅ solids produced by themethod of Example 2 (with 71% P1 and 29% P2) was added to a 100 mL heavywall glass pressure vessel. The pressure vessel was sealed and removedfrom the glovebox. The bottom of the pressure vessel was submerged in apre-heated sand bath at 190° C. or 220° C. for a period of time. Thepressure vessel was then removed from the sand bath and allowed to coolto room temperature for a period of 30 minutes. A big shiny cake wasobserved and it could be easily broken into shining crystalline powdersby shaking the pressure vessel. The pressure vessel was brought backinto the glovebox. Product was collected and submitted for XRD analysisto quantify crystalline phases.

TABLE 6 Sample Temp. (° C.) Time (hr) Ph1 (%) Ph2 (%) W-FG1717 71 29(Starting Materials) 18-001-A 190 1 49 51 18-003-C 3 37 63 18-003-B 2203 22 78 18-004-A 6 16 84The samples having 16% and 22% Phase 1 WCI₅ would be suitable to providea stable vapor supply of WCI₅ vapor during vapor deposition or etchingprocesses.

Example 6: Large Scale Conditioning

FIG. 6 is a schematic diagram of the exemplary equipment in which thisexample was performed. One of ordinary skill in the art will recognizethat the diagram is not to scale (i.e., the 250 mL flask is NOT the samesize as the 4 L cylinder reactor). One of ordinary skill in the art willfurther recognize the sources for the equipment. Some level ofcustomization of the components may be required based upon the desiredtemperature range, pressure range, local regulations, etc.

In a glovebox, 550 g (+/−50 g) grams of freshly sublimed WCI₅ producedby the method of Example 2 (with 17-44% weight Phase 2) was added to a 4L heavy wall glass cylinder reactor 100. The lid 102 was secured to thereactor 100. A security flask 103 was connected to the lid 102 forsafety purposes. More particularly, the security flask 103 captures anyWCI₅ that may escape the reactor 100 due to overheating or other safetyissues. The reactor 100 was heated at 230° C. for a period of 44 (+/−4)his using heating mantle 101. The temperature controller (not shown) wasturned off and the reactor 100 was allowed to slowly cool to below 100°C. inside the heating mantle 101. The reactor 100 was then removed fromthe heating mantle 101. The lid 102 is disassembled and the big shinyblack cake on the bottom of the reactor 100 was poured into the glassmortar. Crystalline powders were obtained by roughly grinding with glassmortar and pestle. Product was collected and submitted for XRT analysisto quantify crystalline phases. Table 7 demonstrates that this processrepeatedly yields product having approximately 70% weight of Phase 2material.

TABLE 7 Batch Phase 1 (weight %) Phase 2 (weight %) 1 28 72 2 28 72 3 2971 4 28 72 5 30 70 6 31 69 7 31 69 8 30 70These materials would be suitable to provide a stable vapor supply ofWCI₅ vapor during a vapor deposition or etching processes.

While embodiments of this invention have been shown and described,modifications thereof can be made by one skilled in the art withoutdeparting from the spirit or teaching of this invention. The embodimentsdescribed herein are exemplary only and not limiting. Many variationsand modifications of the composition and method are possible and withinthe scope of the invention. Accordingly, the scope of protection is notlimited to the embodiments described herein, but is only limited by theclaims which follow, the scope of which shall include all equivalents ofthe subject matter of the claims.

1. A WCI₅-containing composition having 10% weight of WCI₅ to 40% weightof WCI₅ in the form of Phase 1 crystal structure WCI₅ as determined byX-ray diffraction.
 2. The WCI₅-containing composition of claim 1, thecomposition having 10% weight to 35% weight of Phase 1 WCI₅.
 3. TheWCI₅-containing composition of claim 1, the composition having 10%weight to 30% weight of Phase 1 WCI₅.
 4. The WCI₅-containing compositionof claim 1, the composition having 10% weight to 25% weight of Phase 1WCI₅.